Electron transfer at the solid liquid interface; new insights on the mechanism of formation of the grignard reagent

The strong inhibiting effect of trace quantities of selected compounds on the reaction between ultra fine particles of magnesium and alkyl halides in THF strongly suggests that the generally accepted linear mechanism should be replaced by a chain mechanism. The reactivity of batteries of free radical clocks centered on an aliphatic skeleton displays unexpected leaving group effects. Such effects could be rationalized according to a variety of mechanistic schemes. The main ones are: 1) coexistence of polar and electron transfer routes, 2) participation of solvated electrons in the mechanism, 3) gradient of reactivity starting from the magnesium surface to the bulk solution. A series of experiments aiming at a choice between these possibilities is described.     

Synthese de tetrahydrodibenzofurannes : creation d'un carbone quaternaire par transposition de claisen.

A new route to tetrahydrodibenzofurannes is described. It is based upon Claisen transposition of an aryloxycyclohexene to $\text{o}$.hydroxyphenyl cyclohexene which is, in turn, cyclized by palladium acetate. In the studied example, an overall yield of 45 % is obtained in two steps. The isolation of an unexpected minor isomeric transposed compound sets a problem of mechanism.     

Thickness dependent sensing mechanism in sorted semi-conducting single walled nanotube based sensors

Single walled carbon nanotube (SWCNT) networks present outstanding potential for the development of SWCNT-based gas sensors. Due to the complexity of the transport properties of this material, the physical mechanisms at stake during exposure to gas are still under debate. Previously suggested mechanisms are charge transfer between gas molecules and SWCNT and Schottky barrier modulation. By comparing electrical measurements with an analytical model based on Schottky barrier modulation, we demonstrate that one mechanism or the other is predominant depending on the percolation of metallic carbon nanotubes. Below the metallic SWCNT percolation threshold, sensing is dominated by the modulation of the Schottky barrier, while above this threshold, it is only attributed to a charge transfer between SWCNT and gas molecules. Both mechanisms are discussed in terms of sensitivity and resolution leading to routes for the optimization of a gas sensor architecture based on highly enriched semiconducting carbon nanotube films.     

Nucleophilic attack on phosphate diesters: a density functional study of in-line reactivity in dianionic, monoanionic, and neutral systems

A density functional study of the hydrolysis reaction of phosphodiesters with a series of attacking nucleophiles in the gas phase and in solution is presented. The nucleophiles HOH, HO-, CH3OH, and CH3O- were studied in reactions with ethylene phosphate, 2'3'-ribose cyclic phosphate and in their neutral (protonated) and monoanionic forms. Stationary-point geometries for the reactions were determined at the density functional B3LYP/6-31++G(d,p) level followed by energy refinement at the B3LYP/6-311++G(3df,2p) level. Solvation effects were estimated by using a dielectric approximation with the polarizable continuum model (PCM) at the gas-phase optimized geometries. This series of reactions characterizes factors that influence the intrinsic reactivity of the model phosphate compounds, including the effect of nucleophile, protonation state, cyclic structure, and solvent. The present study of the in-line mechanism for phosphodiester hydrolysis, a reaction of considerable biological importance, has implications for enzymatic mechanisms. The analysis generally supports the associative mechanism for phosphate ester hydrolysis. The results highlight the importance for the reaction barrier of charge neutralization resulting from the protonation of the nonbridging phosphoryl oxygens and the role of internal hydrogen transfer in the gas-phase mechanism. It also shows that solvent stabilization has a profound influence on the relative barrier heights for the dianionic, monoanionic, and neutral reactions. The calculations provide a comprehensive data set for the in-line hydrolysis mechanisms that can be used for the development of improved semiempirical quantum models for phosphate hydrolysis reactions.     

Streptavidin chiral stationary phase for the separation of adenosine enantiomers

In this paper, a microbore column packed with streptavidin particles was used, at various temperatures (0-24 degrees C), to separate the adenosine enantiomers by HPLC. Using an aqueous mobile phase, the apparent enantioseparation was high for a small molecule, varying from 11.5 at 0 degrees C to 6.2 at 24 degrees C. From the experiments carried out with a streptavidin-biotin complex stationary phase, it was demonstrated that the blockage of the biotin sites of the immobilized streptavidin was responsible for a strong decrease in the enantioselectivity via a direct and/or an indirect effect. From the analysis of the concentration dependencies of the solute retention factor, it was also shown that a reduction of the D-adenosine specific binding sites occurred at the lowest temperature. The thermodynamic parameters determined from the van't Hoff plots indicated that the D-adenosine binding to the streptavidin specific sites was enthalpically driven.     

Ultrafast electronuclear dynamics of H(2) double ionization

The ultrafast electronic and nuclear dynamics of H(2) laser-induced double ionization is studied using a time-dependent wave packet approach that goes beyond the fixed nuclei approximation. The double ionization pathways are analyzed by following the evolution of the total wave function during and after the pulse. The rescattering of the first ionized electron produces a coherent superposition of excited molecular states which presents a pronounced transient H(+)H(-) character. This attosecond excitation is followed by field-induced double ionization and by the formation of short-lived autoionizing states which decay via double ionization. These two double ionization mechanisms may be identified by their signatures imprinted in the kinetic-energy distribution of the ejected protons.     

The electronic structure of Cu(ethanediimine)+2

Extended-Hückel and multiple-scattering Xα molecular orbital calculations are reported for the Cu(ethanediimine)⁺₂ complex. The results obtained are in agreement. From the calculated electronic transition energies, it is inferred that the lowest excited state is a B₂ state of metal-to-ligand charge-transfer type, confirming resonance Raman results.     

Two-Time-Scale Relaxation Towards Thermal Equilibrium of the Enigmatic Piston

We investigate the evolution of a system composed of N non-interacting point particles of mass m in a container divided into two chambers by a movable adiabatic piston of mass Mm. Using a two-time-scale perturbation approach in terms of the small parameter =2m/(M+m), we show that the evolution towards thermal equilibrium proceeds in two stages. The first stage is a fast, deterministic, adiabatic relaxation towards mechanical equilibrium. The second stage, which takes place at times (M), is a slow fluctuation-driven, diathermic relaxation towards thermal equilibrium. A very simple equation is derived which shows that in the second stage, the position of the piston is given by X _M (t)= L[1/2–(t)] where the function is independent of M. Numerical simulations support the assumptions underlying our analytical derivations and illustrate the large mass range in which the picture holds.